Nonequilibrium bandgap modification in porphyrin-based metal-organic frameworks revealed by transient absorption spectroscopy

IF 3.5 2区物理与天体物理 Q2 PHYSICS, APPLIED

Applied Physics Letters Pub Date : 2024-09-10 DOI:10.1063/5.0218768

Yadong Han, Junhong Yu, Yunfan Yang, Hang Zhang, Zhengbang Wang, Jianbo Hu

{"title":"Nonequilibrium bandgap modification in porphyrin-based metal-organic frameworks revealed by transient absorption spectroscopy","authors":"Yadong Han, Junhong Yu, Yunfan Yang, Hang Zhang, Zhengbang Wang, Jianbo Hu","doi":"10.1063/5.0218768","DOIUrl":null,"url":null,"abstract":"Modifying the equilibrium bandgap has proven to be an effective strategy for optimizing photocarrier properties in metal-organic frameworks (MOFs). In this work, we have investigated the nonequilibrium bandgap modification in cobalt porphyrin-based MOF (Co-TCPP MOF) nanofilms through transient absorption spectroscopy. Our results reveal a captivating redshift–blueshift crossover in the nonequilibrium bandgap of Co-TCPP MOFs, with a staggering maximum shifting value of approximately 170 meV, achieved with an excitation fluence of 96 μJ/cm2. This phenomenon sets the stage for further investigations into harnessing nonequilibrium bandgap modification as a powerful tool for tailoring photocarrier properties. Another key facet of our research is the revelation that the bandgap modification effect observed in Co-TCPP MOFs is strongly dependent on the excitation fluence and is absent in disordered porphyrin molecules. This observation suggests a correlation between the bandgap modification and the amplified many-body interactions present within the ordered MOF structure, thus offering valuable insights into the intricate relationship between bandgap modification, excitation fluence, and ordered MOF structures.","PeriodicalId":8094,"journal":{"name":"Applied Physics Letters","volume":null,"pages":null},"PeriodicalIF":3.5000,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Physics Letters","FirstCategoryId":"101","ListUrlMain":"https://doi.org/10.1063/5.0218768","RegionNum":2,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"PHYSICS, APPLIED","Score":null,"Total":0}

引用次数: 0

Abstract

Modifying the equilibrium bandgap has proven to be an effective strategy for optimizing photocarrier properties in metal-organic frameworks (MOFs). In this work, we have investigated the nonequilibrium bandgap modification in cobalt porphyrin-based MOF (Co-TCPP MOF) nanofilms through transient absorption spectroscopy. Our results reveal a captivating redshift–blueshift crossover in the nonequilibrium bandgap of Co-TCPP MOFs, with a staggering maximum shifting value of approximately 170 meV, achieved with an excitation fluence of 96 μJ/cm2. This phenomenon sets the stage for further investigations into harnessing nonequilibrium bandgap modification as a powerful tool for tailoring photocarrier properties. Another key facet of our research is the revelation that the bandgap modification effect observed in Co-TCPP MOFs is strongly dependent on the excitation fluence and is absent in disordered porphyrin molecules. This observation suggests a correlation between the bandgap modification and the amplified many-body interactions present within the ordered MOF structure, thus offering valuable insights into the intricate relationship between bandgap modification, excitation fluence, and ordered MOF structures.

查看原文本刊更多论文

瞬态吸收光谱揭示卟啉基金属有机框架的非平衡带隙改性

事实证明，改变平衡带隙是优化金属有机框架（MOFs）光载体特性的有效策略。在这项工作中，我们通过瞬态吸收光谱研究了卟啉钴基 MOF（Co-TCPP MOF）纳米薄膜的非平衡带隙修饰。我们的研究结果表明，Co-TCPP MOF 非平衡带隙出现了迷人的 "红移-蓝移 "交叉，在 96 μJ/cm2 的激发通量下，最大位移值约为 170 meV。这一现象为进一步研究利用非平衡带隙改性作为定制光电载体特性的有力工具奠定了基础。我们研究的另一个关键方面是揭示了在 Co-TCPP MOFs 中观察到的带隙修饰效应与激发通量密切相关，而在无序的卟啉分子中则不存在。这一观察结果表明，带隙修饰与有序 MOF 结构中存在的放大多体相互作用之间存在关联，从而为了解带隙修饰、激发通量和有序 MOF 结构之间错综复杂的关系提供了宝贵的见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Applied Physics Letters 物理-物理：应用

CiteScore

6.40

自引率

10.00%

发文量

1821

审稿时长

1.6 months

期刊介绍： Applied Physics Letters (APL) features concise, up-to-date reports on significant new findings in applied physics. Emphasizing rapid dissemination of key data and new physical insights, APL offers prompt publication of new experimental and theoretical papers reporting applications of physics phenomena to all branches of science, engineering, and modern technology. In addition to regular articles, the journal also publishes invited Fast Track, Perspectives, and in-depth Editorials which report on cutting-edge areas in applied physics. APL Perspectives are forward-looking invited letters which highlight recent developments or discoveries. Emphasis is placed on very recent developments, potentially disruptive technologies, open questions and possible solutions. They also include a mini-roadmap detailing where the community should direct efforts in order for the phenomena to be viable for application and the challenges associated with meeting that performance threshold. Perspectives are characterized by personal viewpoints and opinions of recognized experts in the field. Fast Track articles are invited original research articles that report results that are particularly novel and important or provide a significant advancement in an emerging field. Because of the urgency and scientific importance of the work, the peer review process is accelerated. If, during the review process, it becomes apparent that the paper does not meet the Fast Track criterion, it is returned to a normal track.